US20170088458A1 - Low reflective glass member and method for producing low reflective glass member - Google Patents

Low reflective glass member and method for producing low reflective glass member Download PDF

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US20170088458A1
US20170088458A1 US15/373,512 US201615373512A US2017088458A1 US 20170088458 A1 US20170088458 A1 US 20170088458A1 US 201615373512 A US201615373512 A US 201615373512A US 2017088458 A1 US2017088458 A1 US 2017088458A1
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Prior art keywords
low reflective
glass
glass member
porous layer
porosity
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Abandoned
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US15/373,512
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Inventor
Yuichi KUWAHARA
Yohei Kawai
Keisuke Abe
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AGC Inc
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Asahi Glass Co Ltd
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Assigned to ASAHI GLASS COMPANY, LIMITED reassignment ASAHI GLASS COMPANY, LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KUWAHARA, YUICHI, ABE, KEISUKE, KAWAI, YOHEI
Publication of US20170088458A1 publication Critical patent/US20170088458A1/en
Assigned to AGC Inc. reassignment AGC Inc. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: ASAHI GLASS COMPANY, LIMITED
Abandoned legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00Surface treatment of glass, not in the form of fibres or filaments, by etching
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/006Anti-reflective coatings
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21LIGHTING
    • F21VFUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V3/00Globes; Bowls; Cover glasses
    • F21V3/04Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings
    • F21V3/0418
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21LIGHTING
    • F21VFUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V3/00Globes; Bowls; Cover glasses
    • F21V3/04Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings
    • F21V3/06Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings characterised by the material
    • F21V3/061Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings characterised by the material the material being glass

Definitions

  • the present invention relates to a low reflective glass member having reflection of light at the surface suppressed, and a method for producing the low reflective glass member.
  • Patent Document 1 does not disclose that reflection of light is suppressed in the network structure layer of the structure, but discloses that mesh cells of the network structure layer in the structure become gradually smaller in a direction to enter from the surface to the inside. Further, in the production method disclosed in Patent Document 1, in order to form a network structure layer at the surface of a glass substrate, it is necessary to immerse the glass substrate for a long time (e.g. for 7 days) in the aqueous potassium hydrogencarbonate solution.
  • Patent Document 1 JP-A-2013-189351
  • Another object is to provide a method whereby a low reflective glass member having a good appearance can be produced efficiently.
  • the present inventors have investigated whether or not it is possible to suppress reflection of light by the network structure layer as disclosed in Patent Document 1.
  • the network structure layer as disclosed in Patent Document 1.
  • different coloration was observed depending upon the viewing angle or lighting conditions, and reflectance was not sufficiently reduced. It is considered that such appearance problems arose, because the wavelength dependency of reflectance was large with the structure.
  • the present inventors have conducted further researches on etching techniques by paying attention to differences in glass structures depending upon glass compositions and have finally arrived at the present invention.
  • the present invention has the following aspects.
  • a method for producing a low reflective glass member which comprises immersing a glass substrate made of borosilicate glass in an aqueous potassium hydrogencarbonate solution to form a porous layer at the surface of the glass substrate.
  • the porous layer has an inner surface facing the glass substrate, an outer surface opposed to the inner surface, and a virtual intermediate plane, of which the distance from the inner surface and the distance from the outer surface are equal,
  • the porosity of the portion from the outer surface to the intermediate plane of the porous layer is larger by at least 0.1 than the porosity of the portion from the inner surface to the intermediate plane of the porous layer.
  • the expression “ to ” showing a numerical range is used to include the numerical values set forth before and after it as the lower limit value and the upper limit value, respectively. Unless otherwise specified, in the following specification, the expression “ to ” is used to have the same meaning.
  • the low reflective glass member of the present invention has a low light reflectance and good appearance.
  • FIG. 1 is a cross-sectional view showing an example of the low reflective glass member of the present invention.
  • FIG. 2 is a graph of simulation results showing that the wavelength dependency of reflectance becomes small by a porosity inclination in the porous layer.
  • FIG. 3 is a scanning electron micrograph of a cross section near the surface of the low reflective glass member of the present invention.
  • FIG. 4 is a scanning electron micrograph of the surface of the low reflection glass member of the present invention.
  • FIG. 5 is a reflection spectrum at the surface of the porous layer of the low reflective glass member in Ex. 1.
  • FIG. 6 is a reflection spectrum of the surface of the porous layer of the low reflective glass member in Ex. 2.
  • components of the glass are represented by typical oxides such as SiO 2 , B 2 O 3 , etc., and a glass composition is represented by mass percentage based on oxides. In the following, the mass percentage may be expressed simply by %.
  • FIG. 1 is a cross-sectional view showing an example of the low reflective glass member of the present invention
  • FIG. 3 is a scanning electron micrograph of the cross section near the surface of the low reflective glass member
  • FIG. 4 is a scanning electron micrograph of the surface of the low reflective glass member.
  • FIG. 2 is a graph of simulation results showing that the wavelength dependency of reflectance varies depending upon a difference in porosity distribution in the porous layer.
  • the low reflective glass member of the present invention (hereinafter sometimes referred to simply as the glass member) will be described with reference to the drawings, but the present invention is not limited to the illustrated examples.
  • the glass substrate may be laminated on another substrate.
  • the porous layer is preferably formed on both sides of the glass substrates, but it may be formed only on one side.
  • a functional layer other than the porous layer may be provided on one side of the glass substrate.
  • the low reflective glass member 10 has a porous layer 14 at the surface of a glass substrate 12 .
  • the shape of the low reflective glass member 10 may be suitably determined depending upon the application of the low reflective glass member 10 , and is usually a plate shape.
  • the thickness may be suitably determined depending on the application, and is usually from 0.05 to 5.0 mm.
  • the transmittance at a wavelength of 500 nm of the low reflective glass member 10 is preferably at least 94.0%, more preferably at least 96.0%.
  • the low reflective glass member 10 can be suitably used as an optical member.
  • the reflectance at a wavelength of 500 nm at the surface of the porous layer 14 of the low reflective glass member 10 is preferably at most 6.0%, more preferably at most 4.0%.
  • the low reflective glass member 10 can be suitably used as an optical member.
  • the reflectance is a value obtained by a reflectance measurement wherein the non-light incident side surface is not particularly subjected to blackening treatment, i.e. a total value of reflectance at both surfaces.
  • the porous layer 14 has an inner surface facing the glass substrate 12 , an outer surface opposed to the inner surface, and a virtual intermediate plane, of which the distance from the inner surface and the distance from the outer surface are equal, and the porosity of the portion from the outer surface to the intermediate plane (hereinafter sometimes referred to as “porosity of the outer layer”) is larger by at least 0.1 than the porosity of the portion from the inner surface to an intermediate plane (hereinafter sometimes referred to as “porosity of the inner layer”).
  • the porosity of the outer layer is more preferably larger by at least 0.2 than the porosity of the inner layer. Further, it is preferred that the porosity is inclinedly reduced towards the inner surface from the outer surface.
  • the porosity is obtainable by image processing of a scanning electron microscope image of the cross section of the glass member.
  • Patent Document 1 discloses a network structure wherein the mesh becomes gradually smaller in a direction towards inside from the surface.
  • the structure looks such that the porosity of the porous layer is substantially uniform.
  • FIG. 2 is a graph showing simulation results of surface reflectance, in a case (b) where no porosity distribution is present in the porous layer and in a case (c) where the porosity becomes gradually large in 9 stages towards inside from the surface, with respect to the case where a porous layer of 1 mm is present at both front side and backside surfaces, by calculating the refractive index at each wavelength, based on actually measured values (a) of the surface reflectance of a soda-lime glass plate having a thickness of 2 mm.
  • (b) represents the calculation results in the case where a low refractive index layer with a refractive index of 1.23 is present at both front side and backside surfaces of the soda-lime glass plate having a thickness of 2 mm.
  • (c) represents the calculation results in the case where low refractive index layers of the same thickness with refractive indices of 1.23, 1.26, 1.29, 1.32, 1.35, 1.38, 1.41, 1.44 and 1.47, respectively, and with their total thickness being 1 ⁇ m, are present from the surface towards inside, at both front side and backside surfaces of the soda-lime glass plate having a thickness of 2 mm.
  • the wavelength dependency of reflectance is large, the wavelength dependency of transmittance also becomes large, whereby only light with a specific wavelength tends to be strongly reflected or to be well transmitted, to cause a reflection color or different coloration depending upon the viewing angle or application conditions of light.
  • Such coloration becomes a problem, for example, in a case where the low reflective member is to be used as e.g. a cover glass for a solid-state image pickup device (such as a CCD image sensor or a CMOS image sensor).
  • the thickness of the porous layer 14 is preferably from 10 to 100,000 nm, more preferably from 30 to 3,000 nm. When the thickness of the porous layer 14 is at least 10 nm, the reflection of light is suppressed more sufficiently. When the thickness of the porous layer 14 is at most 100,000 nm, the time for immersing the glass substrate in the aqueous potassium hydrogencarbonate solution will not be too long, and the productivity of the low reflective glass member will be better.
  • the thickness of the porous layer 14 is measured from an image obtained by observing a cross section of the low reflective glass member 10 by a scanning electron microscope.
  • the porous layer 14 is, for example, one formed by etching the surface portion of the glass substrate 12 .
  • the porous layer 14 has voids formed by erosion of the glass substrate 12 by the etching solution (e.g. the aqueous potassium hydrogencarbonate solution).
  • the glass substrate 12 is made of borosilicate glass.
  • Borosilicate glass is a glass containing B 2 O 3 and SiO 2 as main components and usually containing alkali metal components, and has a glass structure different from soda lime glass containing Na 2 O, CaO and SiO 2 as main components, alkali-free glass containing Al 2 O 3 and SiO 2 as main components and not containing an alkali metal, or aluminosilicate glass containing Na 2 O, Al 2 O 3 and SiO 2 as main components.
  • borosilicate glass for example, one having the following glass composition is preferred.
  • SiO 2 from 55 to 85%
  • Li 2 O+Na 2 O+K 2 O from 1 to 18%
  • Al 2 O 3 from 0 to 5%.
  • SiO 2 from 65 to 78%
  • Li 2 O+Na 2 O+K 2 O from 1 to 13%
  • Al 2 O 3 from 0 to 5%
  • CaO from 0 to 7%.
  • SiO 2 is a main component of glass, and it is a component to stabilize glass and is essential.
  • the SiO 2 content is preferably at least 55%, more preferably at least 60%, further preferably at least 65%, in order to increase the weather resistance of the glass member.
  • the SiO 2 content is preferably at most 85%, more preferably at most 78%, further preferably at least 70%, since it is thereby easy to form a porous structure by etching treatment.
  • B 2 O 3 is a network former for forming the glass structure together with SiO 2 and thus is essential.
  • the B 2 O 3 content is preferably at least 2%, more preferably at least 5%, further preferably at least 10%, in order to stabilize the glass structure.
  • the B 2 O 3 content is preferably at most 30%, more preferably at most 25%, further preferably at most 20%, in order to increase the weather resistance of the glass member.
  • Li 2 O, Na 2 O and K 2 O are components effective to lower the viscosity of glass and thus to facilitate the production of glass, and at least one of them may be contained.
  • the total content of Li 2 O+Na 2 O+K 2 O is preferably at least 1%, more preferably at least 2%, further preferably at least 4%, since it is thereby possible to facilitate the etching treatment.
  • the total content of Li 2 O+Na 2 O+K 2 O is preferably at most 18%, more preferably at most 13%, further preferably at most 10%, in order to increase the weather resistance of the glass member.
  • Al 2 O 3 is a component to increase the stability of glass and may be contained.
  • its content is preferably at most 8%, more preferably at most 5%, further preferably at most 3%, since it is thereby easy to form a porous structure in which the porosity becomes inclinedly smaller from the surface towards inside by etching treatment.
  • its content is preferably at least 0.1%, more preferably at least 0.5%, in order to increase the stability of glass.
  • CaO may be contained for the purpose of increasing the stability of glass.
  • its content is preferably at most 7%, more preferably at most 5%, in order to make it easy to form a porous structure in which the porosity becomes inclinedly smaller from the surface towards inside by etching treatment.
  • its content is preferably at least 0.1%, more preferably at least 0.5%, for the stability of glass.
  • the borosilicate glass may contain other components to such an extent not to impair the object of the present invention.
  • Such other components may, for example, be MgO, SrO, BaO, ZnO, Li 2 O, Fe 2 O 3 , ZrO 2 , TiO 2 , Y 2 O 3 , CeO 2 , etc.
  • fining agent components such as SO 3 , SnO 2 , Sb 2 O 3 , As 2 O 3 , etc. may be contained.
  • the total content of such other components is preferably at most 15%, more preferably at most 10%.
  • Applications of the low reflective glass member obtainable by the production method of the present invention may, for example, be a cover glass for a solid-state image pickup device (such as a CCD image sensor, or a CMOS image sensor), a cover glass for a light-emitting element in an illumination member, a window glass, etc.
  • a cover glass for a solid-state image pickup device such as a CCD image sensor, or a CMOS image sensor
  • a cover glass for a light-emitting element in an illumination member such as a CCD image sensor, or a CMOS image sensor
  • the method for producing a low reflective glass member of the present invention is a method which comprises immersing the glass substrate in aqueous potassium hydrogencarbonate solution to etch the surface of the glass substrate thereby to form a porous layer at the surface of a glass substrate.
  • the aqueous potassium hydrogencarbonate solution may contain other components in addition to potassium hydrogencarbonate, within a range not to impair the object of the present invention.
  • the concentration of potassium hydrogencarbonate in the aqueous potassium hydrogencarbonate solution is preferably from 0.01 to 5.0 mol/L, more preferably from 0.05 to 3.0 mol/L.
  • concentration of potassium hydrogencarbonate is at least 0.01 mol/L, the etching rate of the glass substrate will be sufficiently fast, and the productivity of the low reflective glass member becomes better.
  • concentration of potassium hydrogencarbonate is at most 5.0 mol/L, the etching rate will be properly controlled, and it will be possible to carry out etching uniformly.
  • the temperature of the aqueous potassium hydrogencarbonate solution is preferably from 30 to 90° C., more preferably from 40 to 85° C., further preferably from 50 to 80° C.
  • the temperature of the aqueous potassium hydrogencarbonate solution is at least 30° C., the etching rate of the glass substrate will be sufficiently fast, and the productivity of the low reflective glass member becomes better.
  • the temperature of the aqueous potassium hydrogencarbonate solution is at most 90° C., no special apparatus will be required, and it will be possible to easily produce a low reflective glass member.
  • the time for immersing the glass substrate in the aqueous potassium hydrogencarbonate solution may vary depending on the concentration of potassium hydrogencarbonate, the temperature of the aqueous potassium hydrogencarbonate solution, etc., but is preferably from 0.5 to 24 hours, more preferably from 1 to 18 hours.
  • the time for immersing the glass substrate in the aqueous potassium hydrogencarbonate solution is at least 0.5 hour, it will be possible to form a porous layer having a sufficient thickness.
  • the productivity of the low reflective glass member will be better.
  • the porous membrane to be formed will have voids, whereby the refractive index of the porous membrane will be low, and the reflection of light will be sufficiently suppressed
  • the glass substrate is borosilicate glass, whereby it is possible to form a porous layer having a sufficient thickness in a short time at the surface of the glass substrate by the aqueous potassium hydrogencarbonate solution, and (iii) the surface of the glass substrate is etched by an aqueous potassium hydrogencarbonate solution, whereby there is no need to use an expensive material. Therefore, it is possible to produce the low reflective glass member with a high productivity at low cost.
  • borosilicate glass is subjected to etching, whereby the porous layer is considered to be such that the porosity of the outer layer is larger than the porosity of the inner layer, and as a result, the wavelength dependency of reflectance is small, and it is possible to obtain a low reflective glass member having good appearance.
  • Ex. 1 and Ex. 3 to 7 are Examples of the present invention, and Ex. 2 and Ex. 8 to 10 are Comparative Examples.
  • the transmission spectrum of a glass substrate before etching and a low reflective glass member after etching was measured by a spectrophotometer (model: U-4100, manufactured by Hitachi High-Technologies Corporation).
  • the scanning speed was set to be 1200 nm/min, and as a light source, a 50W tungsten halogen lamp was used.
  • the sample was brought into contact with the integrating sphere, and diffused light was detected also as the transmitted light.
  • the reflection spectrum at the surface of a glass substrate before etching and a porous layer of a low reflective glass member after etching was measured by a spectrophotometer (model: U-4100, manufactured by Hitachi High-Technologies Corporation).
  • the scanning speed was set to be 1200 nm/min, and as a light source a 50W tungsten halogen lamp was used.
  • the sample was brought into contact with the integrating sphere, and diffused light was detected also as the reflected light.
  • the thickness (physical film thickness) and the porosity of a porous layer were measured from an image obtained by observing the cross section of a low reflective glass member by a scanning electron microscope (model: S-4300, manufactured by Hitachi, Ltd.).
  • the aqueous potassium hydrogencarbonate solution was heated to 70° C. in a water bath, and a glass substrate (length: 7.5 cm, width: 2.5 cm, thickness: 0.3 mm) made of borosilicate glass was immersed for 2 hours in the aqueous potassium hydrogencarbonate solution to etch the surface of the glass substrate.
  • the glass substrate was taken out from the aqueous potassium hydrogencarbonate solution, rinsed with deionized water and dried to obtain a low reflective glass member having a porous layer formed on the entire surface.
  • the glass composition of the borosilicate glass was SiO 2 : 67.8%, B 2 O 3 : 19.6%, Al 2 O 3 : 2.8%, K 2 O: 8.3%, Na 2 O: 0.5%, Li 2 O: 1.0%.
  • the transmission spectrum and reflection spectrum were measured. Further, the thickness of the porous layer, the porosity of the outer layer, the porosity of the inner layer, the porosity difference and the color change were measured.
  • the transmittance at a wavelength of 500 nm, the reflectance at a wavelength of 500 nm, the thickness of the porous layer, the porosity of the outer layer, the porosity of the inner layer, the porosity difference and the color change are shown in Table 1.
  • the reflection spectrum is shown in FIG. 5 .
  • a scanning electron micrograph of the cross section near the surface of the low reflective glass member obtained in Ex. 1 is shown in FIG. 3
  • a scanning electron micrograph of the surface of this low reflective glass member is shown in FIG. 4 .
  • the aqueous potassium hydrogencarbonate solution was heated to 70° C. in a water bath, and a glass substrate (length: 7.5 cm, width: 2.5 cm, thickness: 2.0 mm) made of soda lime glass was immersed for 2 hours in the aqueous potassium hydrogencarbonate solution to etch the surface of the glass substrate.
  • the glass substrate was taken out from the aqueous potassium hydrogencarbonate solution, rinsed with deionized water and dried to obtain a low reflective glass member having a porous layer formed on the entire surface.
  • the glass composition of the soda-lime glass was SiO 2: 71.5 %, Al203: 1.8%, K 2 O: 0.9%, Na 2 O: 12.9%, CaO: 8.7%, MgO: 4.2%.
  • the transmission spectrum and reflection spectrum were measured. Further, the thickness of the porous layer, the porosity of the outer layer, the porosity of the inner layer, the porosity difference and the color change were measured.
  • the transmittance at a wavelength of 500 nm, the reflectance at a wavelength of 500 nm, the thickness of the porous layer, the porosity of the outer layer, the porosity of the inner layer, the porosity difference and the color change are shown in Table 1. Further, the reflection spectrum is shown in FIG. 6 .
  • a low reflective glass member having a porous layer formed on the entire surface was obtained in the same manner as in Ex. 1, except that the potassium hydrogencarbonate concentration, the etch temperature and the etching time were changed as shown in Table 1.
  • the transmission spectrum and reflection spectrum were measured. Further, the thickness of the porous layer, the porosity of the outer layer, the porosity of the inner layer, the porosity difference and the color change were measured.
  • the transmittance at a wavelength of 500 nm, the reflectance at a wavelength of 500 nm, the thickness of the porous layer, the porosity of the outer layer, the porosity of the inner layer, the porosity difference and the color change are shown in Table 1.
  • a low reflective glass member having a porous layer formed on the entire surface was obtained in the same manner as in Ex. 2, except that the potassium hydrogencarbonate concentration, the etch temperature and the etching time were changed as shown in Table 1.
  • the transmission spectrum and reflection spectrum were measured. Further, the thickness of the porous layer, the porosity of the outer layer, the porosity of the inner layer, the porosity difference and the color change were measured.
  • the transmittance at a wavelength of 500 nm, the reflectance at a wavelength of 500 nm, the thickness of the porous layer, the porosity of the outer layer, the porosity of the inner layer, the porosity difference and the color change are shown in Table 1.
  • the transmission spectrum and reflection spectrum were measured. Since no porous layer was formed, the thickness of the porous layer, the porosity of the outer layer, the porosity of the inner layer and the porosity difference were not measured. Further, the color change was measured.
  • the transmittance at a wavelength of 500 nm, the reflectance at a wavelength of 500 nm, the thickness of the porous layer, the porosity of the outer layer, the porosity of the inner layer, the porosity difference and the color change are shown in Table 1. Further, the reflection spectrum is shown by a dotted line as “Before etching” in FIG. 5 .
  • the transmission spectrum and reflection spectrum were measured. Since no porous layer was formed, the thickness of the porous layer, the porosity of the outer layer, the porosity of the inner layer and the porosity difference were not measured. Further, the color change was measured.
  • the transmittance at a wavelength of 500 nm, the reflectance at a wavelength of 500 nm, the thickness of the porous layer, the porosity of the outer layer, the porosity of the inner layer, the porosity difference and the color change are shown in Table 1. Further, the reflection spectrum is shown by a dotted line as “Before etching” in FIG. 6 .
  • the low reflective glass member of the present invention is useful as e.g. a cover glass for a solid-state image pickup device (such as a CCD image sensor or a CMOS image sensor), a cover glass for a light-emitting element in an illumination member, a window glass, etc.
  • a cover glass for a solid-state image pickup device such as a CCD image sensor or a CMOS image sensor
  • a cover glass for a light-emitting element in an illumination member such as a CCD image sensor or a CMOS image sensor

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